Polymerization of olefins

ABSTRACT

Polyolefins made preferably only from ethylene using a selected ethylene oligomerization catalyst to form α-olefins and a polymerization catalyst which can copolymerize ethylene and α-olefins produces a novel polymer which advantageous rheological properties.

This is a continuation-in-part of application Ser. No. 09/273,409 filedMar. 22, 1999, now U.S. Pat. No. 6,214,761, which claims the benefit ofProvisional Application No. 60/117,471 filed Jan. 27, 1999 andProvisional Application No. 60/080,018 filed Mar. 30, 1998.

FIELD OF THE INVENTION

Polymers with varied and useful properties may be produced in processesusing at least two polymerization catalysts, at least one of which is aselected iron or cobalt catalyst, for the synthesis of polyolefins.Novel polymers with improved properties are made using a selectedethylene oligomerization catalyst to form α-olefins and a polymerizationcatalyst capable of copolymerizing ethylene and α-olefins.

TECHNICAL BACKGROUND

Polyolefins are most often prepared by polymerization processes in whicha transition metal containing catalyst system is used. Depending on theprocess conditions used and the catalyst system chosen, polymers, eventhose made from the same monomer(s) may have varying properties. Some ofthe properties which may change are molecular weight and molecularweight distribution, crystallinity, melting point, branching, and glasstransition temperature. Except for molecular weight and molecular weightdistribution, branching can affect all the other properties mentioned.

It is known that certain transition metal containing polymerizationcatalysts containing iron or cobalt, are especially useful inpolymerizing ethylene and propylene, see for instance U.S. patentapplications Ser. No. 08/991372, filed Dec. 16, 1997 now U.S. Pat. No.5,955,555, filed Sep. 21, 1999, and 09/006031, filed Jan. 12, 1998 nowU.S. Pat. No. 6,150,482, filed Nov. 21, 2000 (“equivalents” of WorldPatent Applications 98/27124 and 98/30612). It is also known that blendsof distinct polymers, that vary for instance in molecular weight,molecular weight distribution, crystallinity, and/or branching, may haveadvantageous properties compared to “single” polymers. For instance itis known that polymers with broad or bimodal molecular weightdistributions may often be melt processed (be shaped) more easily thannarrower molecular weight distribution polymers. Also, thermoplasticssuch as crystalline polymers may often be toughened by blending withelastomeric polymers.

Therefore, methods of producing polymers which inherently producepolymer blends are useful especially if a later separate (and expensive)polymer mixing step can be avoided. However in such polymerizations oneshould be aware that two different catalysts may interfere with oneanother, or interact in such a way as to give a single polymer.

Various reports of “simultaneous” oligomerization and polymerization ofethylene to form (in most cases) branched polyethylenes have appeared inthe literature, see for instance World Patent Application 90/15085, U.S.Pat. Nos. 5,753,785, 5,856,610, 5,686,542, 5,137,994, and 5,071,927, C.Denger, et al,. Makromol. Chem. Rapid Commun., vol. 12, p. 697-701(1991), and E. A. Benham, et al., Polymer Engineering and Science, vol.28, p. 1469-1472 (1988). None of these references specifically describesany of the processes herein or any of the branched homopolyethylenesclaimed herein.

SUMMARY OF THE INVENTION

This invention concerns a polyethylene which has one or both of astructural index, S_(T), of about 1.4 or more, and a processabilityindex, P_(R.) of about 40 or more, provided that if S_(T) is less thanabout 1.4, said polymer has fewer than 20 methyl branches per 1000methylene groups.

This invention also concerns a polyethylene which has at least 2branches each of ethyl and n-hexyl or longer and at least one n-butylper 1000 methylene groups, and has fewer than 20 methyl branches per1000 methylene groups, and obeys the equation

[η]<0.0007Mw^(0.63)

wherein [η] is the intrinsic viscosity of said polyethylene in1,2,4-trichlorbenzene at 150° C. and Mw is the weight average molecularweight.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 shows the complex viscosity of polyethylenes, versus frequency ofthe rheometer, as described in Example 30.

FIG. 2 shows the intrinsic viscosity, [η], vs. the weight averagemolecular weight, Mw, for a series of polymers of this invention plusvarious other polymers, which are labeled.

DETAILS OF THE INVENTION

In the polymerization processes and catalyst compositions describedherein certain groups may be present. By hydrocarbyl is meant aunivalent radical containing only carbon and hydrogen. By substitutedhydrocarbyl herein is meant a hydrocarbyl group which contains one ormore (types of) substitutents that does not interfere with the operationof the polymerization catalyst system. Suitable substituents in somepolymerizations may include some or all of halo, ester, keto (oxo),amino, imino, carboxyl, phosphite, phosphonite, phosphine, phosphinite,thioether, amide, nitrile, and ether. Preferred substituents are halo,ester, amino, imino, carboxyl, phosphite, phosphonite, phosphine,phosphinite, thioether, and amide. Which substitutents are useful inwhich polymerizations may in some cases be determined by reference toU.S. patent applications Ser. No. 08/991372, filed Dec. 16, 1997 nowU.S. Pat. No. 5,955,555, filed Sep. 21, 1999, and 09/006031, filed Jan.12, 1998 now U.S. Pat. No. 6,150,482, filed Nov. 21, 2000, (and theircorresponding World Patent Applications), both of which are herebyincluded by reference. By an aryl moiety is meant a univalent groupwhose free valence is to a carbon atom of an aromatic ring. The arylmoiety may contain one or more aromatic ring and may be substituted byinert groups. By phenyl is meant the C₆H₅- radical, and a phenyl moietyor substituted phenyl is a radical in which one or more of the hydrogenatoms is replaced by a substituent group (which may includehydrocarbyl). Preferred substituents for substituted phenyl includethose listed above for substituted hydrocarbyl, plus hydrocarbyl. If nototherwise stated, hydrocarbyl, substituted hydrocarbyl and all othergroups containing carbon atoms, such as alkyl, preferably contain 1 to20 carbon atoms.

By a polymerization catalyst activator is meant a compound that reactswith a transition metal compound to form an active polymerizationcatalyst. A preferred polymerization catalyst activator is analkylaluminum compound, that is a compound which has one or more alkylgroups bound to an aluminum atom.

By a polymerization catalyst component is meant a composition that byitself, or after reaction with one or more other compounds (optionallyin the presence of the olefins to be polymerized), catalyzes thepolymerization of olefins.

Noncoordinating ions are mentioned and useful herein. Such anions arewell known to the artisan, see for instance W. Beck., et al., Chem.Rev., vol. 88, p. 1405-1421 (1988), and S. H. Strauss, Chem. Rev., vol.93, p. 927-942 (1993), both of which are hereby included by reference.Relative coordinating abilities of such noncoordinating anions aredescribed in these references, Beck at p. 1411, and Strauss at p. 932,Table III. Useful noncoordinating anions include SbF₆ ⁻, BAF, PF₆ ⁻, orBF₄ ⁻, wherein BAF is tetrakis [3,5-bis(trifluoromethyl)phenyl] borate.

A neutral Lewis acid or a cationic Lewis or Bronsted acid whosecounterion is a weakly coordinating anion is also present as part of thecatalyst system. By a “neutral Lewis acid” is meant a compound which isa Lewis acid capable of abstracting X from (II) to form a weaklycoordination anion.

In (II), M is Co or Fe, each X is independently and anion and each X issuch that the total negative charges on X equal the oxidation state ofM. The neutral Lewis acid is originally uncharged (i.e., not ionic).Suitable neutral Lewis acids include SbF₅, Ar₃B (wherein Ar is aryl),and BF₃. By a cationic Lewis acid is meant a cation with a positivecharge such as Ag⁺, H⁺, and Na⁺.

In those instances in which (II) does not contain an alkyl or hydridegroup already bonded to the metal (i.e., X is not alkyl or hydride), theneutral Lewis acid or a cationic Lewis or Bronsted acid also alkylatesor adds a hydride to the metal, i.e., causes an alkyl group or hydrideto become bonded to the metal atom, or a separate compound is added toadd the alkyl or hydride group.

A preferred neutral Lewis acid, which can alkylate the metal, is aselected alkyl aluminum compound, such as R⁹ ₃Al, R⁹ ₂AlCl, R⁹AlCl₂, and“R⁹AlO” (alkylaluminoxanes), wherein R⁹ is alkyl containing 1 to 25carbon atoms, preferably 1 to 4 carbon atoms. Suitable alkyl aluminumcompounds include methylaluminoxane (which is an oligomer with thegeneral formula [MeAlO]_(n)), (C₂H₅)₂AlCl, C₂H₅AlCl₂, and[(CH₃)₂CHCH₂]₃Al. Metal hydrides such as NaBH₄ may be used to bondhydride groups to the metal M.

For (I) and (II) preferred formulas and compounds are found in U.S.patent applications Ser. No. 08/991372, filed Dec. 16, 1997 now U.S.Pat. No. 5,955,555, filed Sep. 21, 1999, and 09/006031, filed Jan. 12,1998, now U.S. Pat. No. 6,150,482 and preferred groupings and compoundsin these applications are also preferred herein. However the compoundnumbers and group (i.e., R^(X)) numbers in these applications may varyfrom those herein, but they are readily convertible. These applicationsalso describe synthesis of (I) and (II).

There are many different ways of preparing active polymerizationcatalysts from (I) or (II) many of which are described in U.S. patentapplications Ser. No. 08/991372, filed Dec. 16, 1997 now U.S. Pat. No.5,955,555, filed Sep. 21, 1999, and 09/006031, filed Jan. 12, 1998 nowU.S. Pat. No. 6,150,482, filed Nov. 21, 2000, and those so described areapplicable herein. “Pure” compounds which themselves may be activepolymerization catalysts may be used, or the active polymerizationcatalyst may be prepared in situ by a variety of methods.

For instance, olefins may be polymerized by contacting, at a temperatureof about −100° C. to about +200° C. a first compound W, which is aneutral Lewis acid capable of abstracting X⁻ to form WX⁻, provided thatthe anion formed is a weakly coordinating anion; or a cationic Lewis orBronsted acid whose counterion is a weakly coordinating anion.

Which first active polymerization catalysts will polymerize whicholefins, and under what conditions, will also be found in U.S. patentapplications Ser. No. 08/991372, filed Dec. 16, 1997 now U.S. Pat. No.5,955,555, filed Sep. 21, 1999, and 09/006031, filed Jan. 12, 1998 nowU.S. Pat. No. 6,150,482, filed Nov. 21, 2000, monomers useful herein forthe first active polymerization catalyst include ethylene and propylene.A preferred monomer for this catalyst is ethylene.

In one preferred process described herein the first and second olefinsare identical, and preferred olefins in such a process are the same asdescribed immediately above. The first and/or second olefins may also bea single olefin or a mixture of olefins to make a copolymer. Again it ispreferred that they be identical, particularly in a process in whichpolymerization by the first and second polymerization catalysts makepolymer simultaneously.

In some processes herein the first active polymerization catalyst maypolymerize a monomer that may not be polymerized by said second activepolymerization catalyst, and/or vice versa. In that instance twochemically distinct polymers may be produced. In another scenario twomonomers would be present, with one polymerization catalyst producing acopolymer, and the other polymerization catalyst producing ahomopolymer, or two copolymers may be produced which vary in the molarproportion or repeat units from the various monomers. Other analogouscombinations will be evident to the artisan.

In another variation of the process described herein one of thepolymerization catalysts makes an oligomer of an olefin, preferablyethylene, which oligomer has the formula R⁶⁰CH═CH₂, wherein R⁶⁰ isn-alkyl, preferably with an even number of carbon atoms. The otherpolymerization catalyst in the process (co)polymerizes this olefin,either by itself or preferably with at least one other olefin,preferably ethylene, to form a branched polyolefin. Preparation of theoligomer (which is sometimes called an α-olefin) by a first activepolymerization-type of catalyst can be found in U.S. patent applicationSer. No. 09/005965, filed Jan. 12, 1998 now U.S. Pat. No. 6,103,946,filed Aug. 15, 2000 (“equivalent” of World Patent Application 99/02472),and B. L. Small, et. al., J. Am. Chem. Soc., vol. 120, p. 7143-7144(1998), all of which are hereby included by reference. These referencesdescribe the use of a limited class of compounds such as (II) to preparecompounds of the formula R⁶⁰CH═CH₂ from ethylene, and so would qualifyas a catalyst that produces this olefin. In a preferred version of thisprocess one of these first-type polymerization is used to form theα-olefin, and the second active polymerization catalyst is a catalystwhich is capable of copolymerizing ethylene and olefins of the formulaR^(60 CH═CH) ₂, such as a Ziegler-Natta-type or metallocene-typecatalyst. Other types of such catalysts include transition metalcomplexes of amidimidates and certain iron or cobalt complexes of (I).The amount of branching due to incorporation of the olefin R⁶⁰CH═CH₂ inthe polymer can be controlled by the ratio of α-olefin formingpolymerization catalyst to higher polymer forming olefin polymerizationcatalyst. The higher the proportion of α-olefin forming polymerizationcatalyst the higher the amount of branching. The homopolyethylenes thatare made may range from polymers with little branching to polymers whichcontain many branches, that is from highly crystalline to amorphoushomopolyethylenes. In one preferred form, especially when a crystallinepolyethylene is being made, the process is carried out in the gas phase.It is believed that in many cases in gas phase polymerization when bothcatalysts are present in the same particle on which polymerization istaking place (for example originally a supported catalyst), the α-olefinis especially efficiently used (polymerized into the resulting polymer).When amorphous or only slightly crystalline homopolyethylenes are beingmade the process may be carried out in liquid slurry or solution.

In the variation of the process described in the immediately precedingparagraph a novel homopolyethylene is produced. By “homopolyethylene” inthis instance is meant a polymer produced in a polymerization in whichethylene is the only polymerizable olefin added to the polymerizationprocess in a single step, reactor, or by simultaneous reactions. Howeverit is understood that the polymer produced is not made by the directpolymerization of ethylene alone, but by the copolymerization ofethylene and α-olefins which are produced in situ. The polymer producedusually contains only branches of the formula (excluding endgroups)—(CH₂CH₂)_(n)H wherein n is 1 or more, preferably 1 to 100, morepreferably 1 to 30, of these branches per 1000 methylene atoms. Normallythere will be branches with a range of “n” in the polymer. The amount ofthese branches (as measured by total methyl groups) in the polymerpreferably ranges from about 2 to about 200, especially preferably about5 to about 175, more preferably about 10 to about 150, and especiallypreferably about 20 to about 150 branches per 1000 methylene groups inthe polymer (for the method of measurement and calculation, see WorldPatent Application 96/23010). Another preferable range for thesebranches is about 50 to about 200 methyl groups per 1000 methylenecarbon atoms. It is also preferable (either alone or in combination withthe other preferable features above) that in these branched polymersthere is at least 2 branches each of ethyl and n-hexyl or longer and atleast one n-butyl per 1000 methylene groups, more preferably at least 4branches each of ethyl and n-hexyl or longer and at least 2 n-butylbranches per 1000 methylene groups, and especially preferably at least10 branches each of ethyl and n-hexyl or longer and at least 5 n-butylbranches per 1000 methylene groups. It is also preferred that there aremore ethyl branches than butyl branches in this homopolyethylene. Inanother preferred polymer (alone or in combination with any of the abovepreferred features) there is less than 20 methyl branches, morepreferably less than 2 methyl branch, and especially preferably lessthan 2 methyl branches (all after correction for end groups) per 1000methylene groups.

In the polymerizations to make the “homopolyethylene” only a single highmolecular weight polymer is produced, that is a polymer which has anaverage degree of polymerization of at least 50, more preferably atleast 200, and especially preferably at least 400. The synthesis of thebranched homopolyethylene is believed to be successful in part becausethe catalyst which produces the α-olefin often does so at a ratecomparable with the polymerization rate, both of them, for the sake oflow cost, being relatively rapid.

These homopolyethylenes also have unusual properties, which gives themmuch better processability in processes in which high low shearviscosity and/or low high shear viscose is desirable. For instance, someof the polymers produced by the polymerization herein have unusualTheological properties that make them suitable for the uses describedherein. Using the data shown in FIG. 1, one can calculate certainindices which reflect the improved processing properties. A structuralindex, S_(T), which is defined as

S_(T)=η_(O)/(8.33×10⁻¹⁴)(M_(w))^(3.4)

wherein η_(O) is the zero shear viscosity at 140° C. and M_(w), is theweight average molecular weight of the polymer. Materials that have alarge proportion of carbon atoms in long chain branches as opposed toshort chain branches will have a relatively high S_(T). Preferably thepolymer used herein have an S_(T) of about 1.4 or more, more preferablyabout 2.0 or more. The S_(T) of various polymers in the Examples isgiven in Table 12, at the end of Example 30.

Another index which may be used to measure the potential goodprocessability of a polymer, based on its Theological properties, isP_(R), the Processability Index. This is a shear thinning index, and isdefined as

P_(R)=(η* at 0.00628 rad/s)/(η* at 188 rad/s)

wherein η* is the viscosity at the indicated rate of the viscometer.This is similar to other ratios of vicosities at different shear levels,but covers a broader range of shears. The higher the value of P_(R) thegreater the shear thinning of the polymer. It is preferred that P_(R) ofthe polymers used herein be about 40 or more, more preferably about 50or more, and especially preferably about 100 or more. Furthermore, anycombination of S_(T) and P_(R) values mentioned herein are alsopreferred.

Another way of finding polymers which may have good rheology (andpossibly long chain branching) is the measuring the Mw versus theintrinsic viscosity. Polymers with good processing characteristics willhave a lower intrinsic viscosity for a given Mw versus a (possibly morelinear) worse processing polymer. FIG. 2 shows such relationshipsbetween various polyethylenes and other similar polymers, some of whichare branched. It is clear that the polymers of this invention have lowerintrinsic viscosities for their Mw's than similar “linear”polyethylenes. The line on the right is fitted to the present invention,while the line on the left is fitted to linear polyethylenes orpolyethylenes with short chain branching only, such as typical LLDPEssuch as Exxon's Exceed®. Indeed for the “better” polymers producedherein one could have the relationship

[η]<0.0007Mw^(0.66)

and it is preferred that

[η]<0.0007Mw^(0.63)

Of the two lines shown in FIG. 2, the left hand line is of the equation

[η]=0.00054Mw^(0.69)

while the right hand line is of the equation

[η]=0.00094Mw^(0.60)

For the purposes of these equations, Mw is determined by lightscattering and intrinsic viscosity is determined in1,2,4-trichlorobenzene at 150° C. (see below). The polymers of thepresent invention, especially when they have few methyl groups, andoptionally one or more of the other branching patterns described aboveare thus novel.

Likewise, conditions for such polymerizations, particularly forcatalysts of the first active polymerization type, will also be found inall of these patent applications. Briefly, the temperature at which thepolymerization is carried out is about −100° C. to about +200° C.,preferably about −20° C. to about +80° C. The polymerization pressurewhich is used with a gaseous olefin is not critical, atmosphericpressure to about 275 MPa, or more, being a suitable range. With aliquid monomer the monomer may be used neat or diluted with anotherliquid (solvent) for the monomer. The ratio of W:(I), when W is present,is preferably about 1 or more, more preferably about 10 or more whenonly W (no other Lewis acid catalyst) is present. These polymerizationsmay be batch, semi-batch or continuous processes, and may be carried outin liquid medium or the gas phase (assuming the monomers have therequisite volatility). These details will also be found in U.S. patentapplications Ser. No. 08/991372, filed Dec. 16, 1997 now U.S. Pat. No.5,955,555, filed Sep. 21, 1999, and 09/006031, filed Jan. 12, 1998 nowU.S. Pat. No. 6,150,482, filed Nov. 21, 2000, and 09/005965, filed Jan.12, 1998 now U.S. Pat. No. 6,103,946, filed Aug. 15, 2000.

In these polymerization processes preferred groups for R⁶ is

and for R⁷ is

wherein:

R⁸ and R¹³ are each independently hydrocarbyl, substituted hydrocarbylor an inert functional group;

R⁹, R¹⁰, R¹¹, R¹⁴, R¹⁵ and R¹⁶ are each independently hydrogen,hydrocarbyl, substituted hydrocarbyl or an inert functional group;

R¹² and R¹⁷ are each independently hydrogen, hydrocarbyl, substitutedhydrocarbyl or an inert functional group;

and provided that any two of R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶and R¹⁷ that are vicinal to one another, taken together may form a ring.

Two chemically different active polymerization catalysts are used in thepolymerization described herein. The first active polymerizationcatalyst is described in detail above. The second active polymerizationcatalyst may also meet the limitations of the first activepolymerization catalyst, but must be chemically distinct. For instance,it may have a different transition metal present, and/or utilize aligand which differs in structure between the first and second activepolymerization catalysts. In one preferred process, the ligand type andthe metal are the same, but the ligands differ in their substituents.

Included within the definition of two active polymerization catalystsare systems in which a single polymerization catalyst is added togetherwith another ligand, preferably the same type of ligand, which candisplace the original ligand coordinated to the metal of the originalactive polymerization catalyst, to produce in situ two differentpolymerization catalysts.

However other types of catalysts may also be used for the second activepolymerization catalyst. For instance so-called Ziegler-Natta and/ormetallocene-type catalysts may also be used. These types of catalystsare well known in the polyolefin field, see for instance Angew. Chem.,Int. Ed. Engl., vol. 34, p. 1143-1170 (1995), European PatentApplication 416,815 and U.S. Pat. No. 5,198,401 for information aboutmetallocene-type catalysts, and J. Boor Jr., Ziegler-Natta Catalysts andPolymerizations, Academic Press, New York, 1979 for information aboutZiegler-Natta-type catalysts, all of which are hereby included byreference. Suitable late metal transition catalysts will be found inWorld Patent Applications 96/23010 and 97/02298, both of which arehereby included by reference. Many of the useful polymerizationconditions for these types of catalyst and the first activepolymerization catalysts coincide, so conditions for the polymerizationswith first and second active polymerization catalysts are easilyaccessible. Oftentimes the “co-catalyst” or “activator” is needed formetallocene of Ziegler-Natta-type polymerizations, much as W issometimes needed for polymerizations using the first activepolymerization catalysts. In many instances the same compound, such asan alkylaluminum compound, may be used for these purposes for both typesof polymerization catalysts.

Suitable catalysts for the second polymerization catalyst also includemetallocene-type catalysts, as described in U.S. Pat. No. 5,324,800 andEuropean Patent Application 129,368; particularly advantageous arebridged bis-indenyl metallocenes, for instance as described in U.S. Pat.No. 5,145,819 and European Patent Application 485,823. Another class ofsuitable catalysts comprises the well-known constrained geometrycatalysts, as described in European Patent Applications 416,815,420,436, 671,404, and 643,066 and World Patent Application 91/04257.Also the class of transition metal complexes described in WO96/13529 canbe used. Also useful are transition metal complexes ofbis(carboximidamidatonates), as described in U.S. patent applicationSer. No. 08/096668, filed Sep. 1, 1998.

All the catalysts herein may be “heterogenized” (to form apolymerization catalyst component, for instance) by coating or otherwiseattaching them to solid supports, such as silica or alumina. Where anactive catalyst species is formed by reaction with a compound such as analkylaluminum compound, a support on which the alkylaluminum compound isfirst coated or otherwise attached is contacted with the transitionmetal compounds (or their precursors) to form a catalyst system in whichthe active polymerization catalysts are “attached” to the solid support.These supported catalysts may be used in polymerizations in organicliquids. They may also be used in so-called gas phase polymerizations inwhich the olefin(s) being polymerized are added to the polymerization asgases and no liquid supporting phase is present. The transition metalcompounds may also be coated onto a support such as a polyolefin(polyethylene, polypropylene, etc.) support, optionally along with otherneeded catalyst components such as one or more alkylaluminum compounds.

The molar ratio of the first active polymerization catalyst to thesecond active polymerization catalyst used will depend on the ratio ofpolymer from each catalyst desired, and the relative rate ofpolymerization of each catalyst under the process conditions. Forinstance, if one wanted to prepare a “toughened” thermoplasticpolyethylene that contained 80% crystalline polyethylene and 20% rubberypolyethylene, and the rates of polymerization of the two catalysts wereequal, then one would use a 4:1 molar ratio of the catalyst that gavecrystalline polyethylene to the catalyst that gave rubbery polyethylene.More than two active polymerization catalysts may also be used if thedesired product is to contain more than two different types of polymer.

The polymers made by the first active polymerization catalyst and thesecond active polymerization catalyst may be made in sequence, i.e., apolymerization with one (either first or second) of the catalystsfollowed by a polymerization with the other catalyst, as by using twopolymerization vessels in series. However it is preferred to carry outthe polymerization using the first and second active polymerizationcatalysts in the same vessel(s), i.e., simultaneously. This is possiblebecause in most instances the first and second active polymerizationcatalysts are compatible with each other, and they produce theirdistinctive polymers in the other catalyst's presence.

The polymers produced by this process may vary in molecular weightand/or molecular weight distribution and/or melting point and/or levelof crystallinity, and/or glass transition temperature or other factors.For copolymers the polymers may differ in ratios of comonomers if thedifferent polymerization catalysts polymerize the monomers present atdifferent relative rates. The polymers produced are useful as moldingand extrusion resins and in films as for packaging. They may haveadvantages such as improved melt processing, toughness and improved lowtemperature properties.

In the Examples, all pressures are gauge pressures.

In the Examples the transition metal catalysts were either bought, or ifa vendor is not listed, were made. Synthesis of nickel containingcatalysts will be found in World Patent Application 96/23010, whilesynthesis of cobalt and iron containing catalysts will be found in U.S.patent applications Ser. No. 08/991372, filed Dec. 16, 1997 now U.S.Pat. No. 5,955,555, filed Sep. 21, 1999 and 09/006031, filed Jan. 12,1998 now U.S. Pat. No. 6,150,482, filed Nov. 21, 2000.

In the Examples PMAO-IP is a form of methylaluminoxane which stays insolution in toluene, and is commercially available. W440 is aZiegler-Natta type catalyst of unknown structure available from AkzoChemicals, Inc., 1 Livingston Ave., Dobbs Ferry, N.Y. 10522, U.S.A.

EXAMPLES 1-AND COMPARATIVE EXAMPLES A-E

Ethylene Polymerization General Procedure

The catalyst was weighed into a reaction vessel and was dissolved inabout 20 mL of distilled toluene. The reaction was sealed andtransferred from the drybox to the hood. The reaction was purged withnitrogen, then ethylene. The PMAO-IP (methylaluminoxane solution) wasthen quickly added to the vessel and the reaction was put under 35 kPaethylene. The reaction ran at room temperature in a water bath to helpdissipate heat from any exotherm. The ethylene was then turned off andthe reaction was quenched with about 15 mL of methanol/HCl solution(90/10 volume %). If polymer was present, the reaction was filtered andthe polymer was rinsed with methanol, then acetone and dried overnightin the hood. The resulting polymer was collected and weighed.

Below for each polymerization the catalysts used are listed:

EXAMPLE 1

catalyst 1: 4 mg (0.006 mmol)

catalyst 2: Zirconocene dichloride, from Strem Chemicals, catalog#93-4002, 2 mg (0.006 mmol)

co-catalyst: PMAO-IP; 2.0 mmole Al; 1.0 mL of 2.0M in toluene

duration: 4 h

polymer: 5.322 g yield

EXAMPLE 2

catalyst 1: 4 mg (0.006)

catalyst 2: 4 mg (0.006)

cocatalyst: PMAO-IP; 2.0 mmol Al; 1.0 mL of 2.0M in toluene

duration: 4 h

polymer: 2.282 g yield

EXAMPLE 3

catalyst 1: 3.5 mg (0.006 mmol)

catalyst 2: Zirconocene dichloride, from Strem Chemicals, catalog#93-4002, 2 mg (0.006 mmol)

cocatalyst: PMAO-IP; 2.0 mmol Al; 1.0 mL of 2.0M in toluene

duration: 4 h

polymer: 3.651 g yield

EXAMPLE 4

catalyst 1: 3.5 mg (0.006 mmole)

catalyst 2: 4 mg (0.006 mmol)

cocatalyst: PMAO-IP; 2.0 mmol Al; 1.0 mL of 2.0M in toluene

duration: 4 h

polymer: 2.890 g yield

EXAMPLE 5

catalyst 1: 3.5 mg (0.006 mmol)

catalyst 2: 4 mg (0.006 mmol)

cocatalyst: PMAO-IP; 2.0 mmole Al; 1.0 mL of 2.0M in toluene

duration: 4 h

polymer: 3.926 g yield

EXAMPLE 6

catalyst 1: 4 mg (0.006 mmol)

catalyst 2: W440, from Akzo Nobel, 2.3 wt % Ti, 12 mg (0.006 mmole ofTi, based on wt %) cocatalyst: PMAO-IP; 2.0 mmole Al; 1.0 mL of 2.0M intoluene

duration: 4 h

polymer: 2.643 g yield

EXAMPLE 7

catalyst 1: 3.5 mg (0.006 mmol)

catalyst 2: W440, from Akzo Nobel, 2.3 wt % Ti, 12 mg (0.006 mmole ofTi, based on wt %)

cocatalyst: PMAO-IP; 2.0 mmol Al; 1.0 mL of 2.0M in toluene

duration: 4 h

polymer: 2.943 g yield

EXAMPLE 8

catalyst 1: 4 mg (0.006 mmol)

catalyst 2: 4 mg (0.006 mmol)

catalyst 3: Zirconocene dichloride, from Strem Chemicals, catalog#93-4002, 2 mg (0.006 mmol)

cocatalyst: PMAO-IP; 3.0 mmol Al; 1.5 mL of 2.0M in toluene

duration: 4 h

polymer: 6.178 g yield

EXAMPLE 9

catalyst 1: 3.5 mg (0.006 mmol)

catalyst 2: 4 mg (0.006 mmol)

catalyst 3: Zirconocene dichloride, from Strem Chemicals, catalog#93-4002, 2 mg (0.006 mmol)

cocatalyst: PMAO-IP; 3.0 mmol Al; 1.5 mL of 2.0M in toluene

duration: 4 h

polymer: 4.408 g yield

Comparative Example A

catalyst: Zirconocene dichloride, from Strem Chemicals, catalog#93-4002, 2 mg (0.006 mmol)

cocatalyst: PMAO-IP; 1.0 mmol Al; 0.5 mL of 2.0M in toluene

duration: 4 h

polymer: 2.936 g yield

Comparative Example B

catalyst: 4 mg (0.006 mmol)

cocatalyst: PMAO-IP; 1.0 mmol Al; 0.5 mL of 2.0M in toluene

duration: 4 h

polymer: 1.053 g yield

Comparative Example C

catalyst: 4 mg (0.006 mmol)

cocatalyst: PMAO-IP; 1.0 mmol Al; 0.5 mL of 2.0M in toluene

duration: 4 h

polymer: 2.614 g yield

Comparative Example D

catalyst: 3.5 mg (0.006 mmol)

cocatalyst: PMAO-IP; 1.0 mmol Al; 0.5 mL of 2.0M in toluene

duration: 4 h

polymer: 2.231 g yield

Comparative Example E

catalyst: W440, from Akzo Nobel, 2.3 wt % Ti, 12 mg (0.006 mmole of Ti,based on wt %)

cocatalyst: PMAO-IP; 1.0 mmol Al; 0.5 mL of 2.0M in toluene

duration: 4 h

polymer: 0.326 g yield

EXAMPLES 10-12

Propylene Polymerization General Procedure

The catalyst was weighed into a reaction vessel and was dissolved inabout 20 mL of distilled toluene. The reaction was sealed andtransferred from the drybox to the hood. The reaction was purged withnitrogen, then propylene. The MAO was then quickly added to the vesseland the reaction was put under 35 kPa propylene. Reaction ran at 0° C.in an ice bath. The propylene was then turned off and the reaction wasquenched with about 15 mL of methanol/HCl solution (90/10 volume %). Ifpolymer was present, the reaction was filtered and the polymer wasrinsed with methanol, then acetone and dried overnight in the hood. Theresulting polymer was collected and weighed.

EXAMPLE 10

catalyst 1: 3 mg (0.006 mmol)

catalyst 2: Zirconocene dichloride, from Strem Chemicals, catalog#93-4002, 2 mg (0.006 mmol)

cocatalyst: PMAO-IP; 2.0 mmol Al; 1.0 mL of 2.0M in toluene

duration: 5 h

polymer: 0.471 g yield

EXAMPLE 11

catalyst 1: 3 mg (0.006 mmol)

catalyst 2: 4 mg (0.006 mmol)

cocatalyst: PMAO-IP; 2.0 mmole Al; 1.0 mL of 2.0M in toluene

duration: 5 h

polymer: 1.191 g yield

EXAMPLE 12

catalyst 1: 3 mg (0.006 mmol)

catalyst 2: W440, from Akzo Nobel, 2.3 wt % Ti, 12mg (0.006 mmole of Ti,based on wt %)

cocatalyst: PMAO-IP; 2.0 mmol Al; 1.0 mL of 2.0M in toluene

duration: 5 h

polymer: 0.238 g yield

EXAMPLES 13-77 AND COMPARATIVE EXAMPLES F-N

In these Examples, compounds A-V and 2 were used as the transition metalcompounds.

For preparation of: compound A see B. L. Small, et al., J. Am. Chem.Soc., vol. 120, p. 7143-7144(1998); compound B see Ewen, et al., J. Am.Chem. Soc., vol. 110, p. 6255-6256(1988); compound C see European PatentApplication 416,815; compound D World patent Application 98/27124;compound E World patent Application 96/23010; compounds G, H, I and Rwere purchased from Boulder Scientific company; 10 compounds K, P and 2were bought from Strem Chemicals Inc.; compound Q was obtained fromAldrich Chemical Co.; compounds S, T, U and V were made by proceduresdescribed in U.S. patent application Ser. No. 08/096668, filed Sep. 1,1998 now U.S. Pat. No. 5,337,529 Aug. 16, 1999; compound F was made byreacting ZrCl₄ and the amide lithium salt (see J. Chem. Soc., DaltonTrans. 1994, 657) in ether overnight, and removing the ether and pentaneextraction gave F 69% yield; compound J was prepared by modifying theprocedure of Journal of Organometallic Chemistry 1993, 459, 117-123;compounds L and M were prepared by following the preparation inMacromolecules, 1995, 28, 5399-5404, and Journal of OrganometallicChemistry 1994, 472, 113-118; compound N was made by the proceduredescribed in U.S. Pat. No. 5,096,867; and compound O was prepared byfollowing a literature procedure (Ferdinand R. W. P. Wild, et al.,Journal of Organometallic Chemistry 1985, 288, 63-67).

EXAMPLES 13-17 AND COMPARATIVE EXAMPLES F-G

A 600 mL Parr® reactor was heated up under vacuum and then allowed tocool under nitrogen. In a drybox, to a Hoke® cylinder was added 5 mLtoluene and a certain amount of PMAO-IP (13.5wt % toluene solution) asshown in Table 1. To a 20 mL vial was added the ethylene(co)polymerization catalyst and 2 mL toluene. The solution was thenpipette transferred to a 300 mL RB flask, followed by addition of 150 mL2,2,4-trimethyl pentane. If catalyst A was used, its toluene suspensionwas syringe transferred to the flask. The flask was capped with a rubbersepta. Both the Hoke® cylinder and the flask were brought out of thedrybox. Under nitrogen protection, the transition metal compoundsolution was cannulated to the reactor. The reactor was pressurized withnitrogen and then the nitrogen was released. The reactor was heated to70° C., then, pressurized 2× to 690 kPa ethylene, venting each time andfinally pressurized to 970 kPa with stirring. The MAO solution was addedfrom the Hoke® cylinder at slightly higher pressure. The ethylenepressure of the reactor was then adjusted to the desired pressure (Table1). The reaction mixture was allowed to stir for certain period of time(Table 1). The heating source was removed. Ethylene was vented to about210 kPa. The reactor was back filled with 1.4 MPa nitrogen and was thenvented to 210 kPa. This was repeated once. The reaction mixture was thencooled to RT (room temperature). The reaction mixture was then slowlypoured into 400 mL methanol, followed by addition of 6 mL conc. HCl.Upon stirring at RT for 25 min, polymer was filtered, washed withmethanol six times and dried in vacuo.

EXAMPLES 18-76 (EXCEPT EXAMPLES 22 AND 23) AND COMPARATIVE EXAMPLES H-N

General procedure for making silica supported catalysts: In a drybox,one of transition metal compounds (but not A), and compound A (0.1 wt %in biphenyl) and silica supported MAO (18 wt % in Al, Albermarle) weremixed with 15 mL of toluene in a 20 mL vial. The vial was shaken for 45minutes at RT. The solid was filtered, washed with 3×5 mL toluene anddried in vacuo for 1 hour. It was then stored in a freezer in the dryboxand was used the same day.

General procedure for gas phase ethylene polymerization by the supportedcatalysts using a multitube block reactor: In a drybox, supportedcatalysts (5.0 mg or 2.0 mg each, except Example 20 where 15.0 mg wasused) were weighed in GC vials. They were placed in a Harper BlockReactor. The reactor was brought out of the drybox and was charged with1.21 MPa of ethylene. It was then placed in a 90° C. oil bath for 1 hunder 1.12 MPa of ethylene. The reactor temperature reached 85° C. after23 minutes and 87° C. after 35 min. The temperature stayed at 87°C. forthe rest of the reaction. (Time, temperature and pressure for Examplesin Tables 7-9, as noted.) Ethylene was vented. Polymers were weighed andthen submitted for ¹H NMR analysis(TCE-d₂, 120° C.) withoutpurification. Details of these polymerizations are given in Table 2-9.

In Table 10, the branching distribution [in branches per 1,000 methylene(CH₂) groups] of the product polymers of selected examples are given.They were determined by ¹³C NMR (TCB, 120° C.). Methods for measuringthe branching distribution are found in World patent Application96/23010.

In all the Tables, where provided, branching levels in the polymers,Me/1000CH₂ groups, methyl groups per 1000 methylene groups in thepolymer, are measured by the method described in World PatentApplication 96/23010. In the Tables PE is polyethylene, TON is moles ofethylene polymerized/mole of polymerization catalysts (total oftransition metal compounds present)/h, Mn is number average molecularweight, PDI is Mw/Mn where Mw is weight average molecular weight, and Pis ethylene pressure. The PMAO-IP used was 13.5 wt. % in toluene. Theamount of residual α-olefin in the polymer was estimated by ¹H NMR, bymeasurement of the vinylic proton signals of the α-olefin.

TABLE 1 Catalyst, amount Catalyst A Ex. (×10⁻⁶ (×10⁻⁶ P_(C2H4) Time MMAOPE yield #Me Per m.p. Density(IR) No. mole) mole) MPa T(° C.) (min.)(mL) (g) 1000CH₂ (° C.) Mn/PDI (g/cm³) F B, 8.1 0 1.21  70-100 35 4.215.0 1 134 43,700/2.2 0.952 13 B, 8.1 0.26 1.31 81-96 25 4.2 24.0 17116, 103 32,400/2.2 0.914 G C, 2.2 0 1.1 90 30 1.2 11.0 4 13211,700/19.7 0.940 14 C, 9.5 0.06 1.31 109-126 30 4.8 31.2 8 133125,000/2.7 0.937 15 C, 9.5 0.13 1.34  80-120 36 4.8 30.0 11 11968,400/2.5 0.922 16 C, 4.6 0.26 1.3 71-96 25 2.4 10.3 45 121, 5694,000/2.3 0.895 261/2.8* 17 C, 3.0 2.3 1.41 100-116 43 1.5 16.6 52 117,98 65,000/2.1 0.922 84 214/3.4* *Bimodal distribution due to α-olefins

TABLE 2 Catalyst and PE Ex. amount Catalyst A Al:M:Fe ratio yield Tm No.(×10⁻⁶ mole) (×10⁻⁶ mole) M = Zr, Ti or Fe (g) #Me/1000CH₂ (° C.) Mn/PDITON H B, 0.033 0 1000:1:0   0.195 5 127 24,039/5.2 210,000 I C, 0.033 01000:1:0   0.075 4 126 125,451/2.1  82,000 18 B, 0.033 0.001 1000:1:0.030.485 15 120 48,213/4.1 500,000 19 B, 0.033 0.0033 1000:1:0.1  0.159 62125 1,916/24.0 150,000 20 C, 0.099 0.0030 1000:1:0.03 0.200 35 11363,534/2.7  70,000 21 D, 0.033 0.0017 1000:1:0.05 0.228 4 133 2,150/26.2240,000

TABLE 3 Catalyst A PE Ex. amount Catalyst A Al:M:Fe ratio yield No.(×10⁻⁶ mole) (×10⁻⁶ mole) M = Ar, Ti or Fe (g) #Me/1000CH₂ TON J H,0.033 0 1000:1:0 0.421 2 460,000 K I, 0.033 0 1000:1:0 0.135 4 150,000 LG, 0.033 0 1000:1:0 0.420 2 460,000 M K, 0.033 0 1000:1:0 0.091 3 99,000 N R, 0.033 0 1000:1:0 0.203 2 220,000

TABLE 4 Catalyst and PE α-olefins Ex. amount Catalyst A Al:M:Fe ratioyield #Me/ Tm left in No. (×10⁻⁶ mole) (×10⁻⁶ mole) M = Zr, Ti or Fe (g)1000CH₂ (° C.) Mn/PDI TON polymer 24 F, 0.033 0.0017 1000:1:0.05 0.07366 120 213/18.5  76,000 significant 25 G, 0.033 0.0017 1000:1:0.05 0.50313 122, 115 41,525/4.7 520,000 almost none 26 H, 0.033 0.00171000:1:0.05 0.752 9 120, 115 54,825/4.7 780,000 almost none 27 I, 0.0330.0017 1000:1:0.05 0.562 31 119 72,982/3.2 580,000 almost none 28 J,0.033 0.0017 1000:1:0.05 0.032 54 — 895/5.6  33,000 small amount 29 K,0.033 0.0017 1000:1:0.05 0.240 16 123 1,124/16.5 250,000 small amount 30L, 0.033 0.0017 1000:1:0.05 0.112 75 116, 102 — 116,000 significant 31M, 0.033 0.0017 1000:1:0.05 0.092 61 119 —  96,000 significant 32 N,0.033 0.0017 1000:1:0.05 0.068 75 124 485/18.3  71,000 small amount 33O, 0.033 0.0017 1000:1:0.05 0.024 15 — —  25,000 almost none 34 P, 0.0330.0017 1000:1:0.05 0.019 12 — —  20,000 small amount 35 Q, 0.033 0.00171000:1:0.05 0.082 40 — —  85,000 significant 36 2, 0.033 0.00171000:1:0.05 0.157 7 — — 160,000 — 37 R, 0.033 0.0017 1000:1:0.05 0.41610 122 37,993/7.3 450,000 almost none 38 S, 0.033 0.0017 1000:1:0.050.056 59 — —  58,000 significant 39 T, 0.033 0.0017 1000:1:0.05 0.023 73— —  24,000 significant 40 U, 0.033 0.0017 1000:1:0.05 0.102 69 — —110,000 significant 41 V, 0.033 0.0017 1000:1:0.05 0.059 78 — —  61,000significant

TABLE 5* Catalyst and PE α-olefins Ex. amount Catalyst A Al:M:Fe ratioYield #Me/ left in No. (×10⁻⁶ mole) (×10⁻⁶ mole) M = Zr, Ti or Fe (g)1000CH₂ Mn/PDI TON polymer 42 D, 0.033 0.0033 1000:1:0.10 0.481 83,346/48.6 360,000 significant 43 D, 0.033 0.0082 1000:1:0.25 0.534 14402/156.0 350,000 significant 44 D, 0.033 0.016 1000:1:0.50 0.566 20800/103.0 310,000 significant *Reaction time here is 80 minutes

TABLE 6 Catalyst and PE Ex. amount Catalyst A Al:M:Fe ratio yield #Me/Tm Density No. (×10⁻⁶ mole) (×10⁻⁶ mole) M = Zr, Ti or Fe (g) 1000CH₂ (°C.) Mn/PDI TON (g/cm³) 45 H, 0.033 0.0017 1000:1:0.05 0.772 6 12443,791/6.0 800,000 0.930 46 H, 0.013 0.0007 1000:1:0.05 0.367 8 12482,151/3.7 950,000 — 47 I, 0.033 0.0017 1000:1:0.05 0.566 38 11470,462/4.0 590,000 0.909 48 I, 0.013 0.0007 1000:1:0.05 0.226 32 — —590,000 — 49 B, 0.033 0.0010 1000:1:0.03 0.442 8 127 52,67314.9 460,0000.928 50 B, 0.033 0.0010 1000:1:0.03 0.563 17 120 52,350/4.9 600,000 —51 B, 0.013 0.0004 1000:1:0.03 0.134 16 — — 350,000 — 52 R, 0.033 0.00101000:1:0.03 0.699 — — — 740,000 — 53 N, 0.013 0.0004 1000:1:0.03 0.362 6124 55,102/5.0 960,000 — 54 I, 0.033 0.0010 1000:1:0.03 0.376 15 11898,599/4.0 400,000 — 55 G, 0.033 0.0010 1000:1:0.03 0.665 5 12438,693/6.0 700,000 —

TABLE 7* Catalyst and PE Ex. amount Catalyst A Al:M:Fe ratio Yield #Me/Tm No. (×10⁻⁶ mole) (×10⁻⁶ mole) M = Zr, Ti or Fe (g) 1000CH₂ (° C.)Mn/PDI TON 56 B, 0.033 0.0017 1000:1:0.05 0.740 22 118,101 54,573/4.0380,000 57 B, 0.013 0.0007 1000:1:0.05 0.206 24 — — 270,000 58 H, 0.0330.0017 1000:1:0.05 1.158 7 121 92,063/4.9 600,000 59 H, 0.013 0.00071000:1:0.05 0.651 12 — — 850,000 60 I, 0.033 0.0017 1000:1:0.05 0.439 24102 102,798/3.8 230,000 61 I, 0.013 0.0007 1000:1:0.05 0.390 25 — —510,000 62 G, 0.033 0.0017 1000:1:0.05 0.871 9 121 45,311/4.7 450,000*Two h at 70° C. and 2.4 MPa ethylene pressure.

TABLE 8* Catalyst and PE Ex. amount Catalyst A Al:M:Fe ratio yield No.(×10⁻⁶ mole) (×10⁻⁶ mole) M = Zr, Ti or Fe (g) TON 63 B, 0.013 0.00071000:1:0.05 0.143 370,000 64 B, 0.013 0.0007 1000:1:0.05 0.115 300,00065 H, 0.013 0.0007 1000:1:0.05 0.305 790,000 66 H, 0.013 0.00071000:1:0.05 0.215 560,000 67 I, 0.013 0.0007 1000:1:0.05 0.093 240,00068 I, 0.013 0.0007 1000:1:0.05 0.108 280,000 69 G, 0.013 0.00071000:1:0.05 0.349 900,000 One h at 90° C. at 2.4 MPa ethylene pressure.

TABLE 9* Catalyst and PE Ex. amount Catalyst A Al:M:Fe ratio yield #Me/No. (×10⁻⁶ mole) (×10⁻⁶ mole) M = Zr, Ti or Fe (g) 1000CH₂ Mn/PDI TON 70B, 0.033 0.0017 1000:1:0.05 0.534 37 42,448/3.4 280,000 71 B, 0.0330.0017 1000:1:0.05 0.489 45 — 250,000 72 H, 0.033 0.0017 1000:1:0.050.969 17 77,142/4.8 500,000 73 H, 0.033 0.0017 1000:1:0.05 1.027 11 —530,000 74 I, 0.033 0.0017 1000:1:0.05 0.442 34 96,383/4.2 230,000 75 I,0.033 0.0017 1000:1:0.05 0.466 32 — 240,000 76 G, 0.033 0.00171000:1:0.05 0.710 8 39,693/4.9 370,000 *Two h at 60° C., 2.4 MPaethylene pressure

TABLE 10 Ex. No. Total Me Me Et Pr Bu Am Hex and higher 15 10.5 0 4.6 02.4 0 4.3 13 16 0 6.5 0 3.2 0 6.5 26 6.9 0 2.9 0 0.4 0 2.5 47 23 0 8.6 04.7 0 10.7 49 8.1 0 3.6 0 1.3 0 3.1

EXAMPLE 22

In a drybox, 1.7 mg Compound E and 1.0 mg Compound A were mixed with 40mL toluene in a Schlenk flask. This was brought out of the drybox andwas purged with ethylene for 15 min at 0° C. MAO toluene solution (0.64mL 13.5 wt %) was injected. The mixture was allowed to stir under 0 kPaethylene at 0° C. for 12 min. Methanol (100 mL) was injected, followedby 1 mL conc. HCl. Upon stirring for 25 min at RT, the white solid wasfiltered, washed with 6×20 mL methanol and dried in vacuo. White solid(2.9 g) was obtained. ¹HNMR in TCE-d₂ at 120° C.: 44Me/1000CH₂. Thepolymer contained a significant amount of α-olefins.

EXAMPLE 23

In a drybox, 30.5 mg of Compound A was mixed with 30.5 g biphenyl in a100 mL Pyrex® glass bottle. This was stirred in a 100° C. bath for 25minutes, during which time Compound A dissolved in biphenyl to form adeep green solution. The solution was allowed to cool down to becomesolid. A 0.1 wt % Compound A/biphenyl homogeneous mixture was obtained.

EXAMPLE 24

A 600 mL Parr® reactor was heated up under vacuum and then allowed tocool under nitrogen. In a drybox, to a 300 mL RB flask was added 150 mL2,2,4-trimethylpentane. The flask was capped with a rubber septum. Theflask was brought out of the drybox. Under nitrogen protection, the2,2,4-trimethylpentane solvent was cannulated into the reactor. Thereactor was pressured up with nitrogen and then nitrogen was released.This was repeated one more time. The reactor was heated to 70° C. Thenin a drybox, 160 mg supported catalyst(made by following the generalprocedure of preparing silica supported catalysts, it contained 0.0011mmole of compound B, 0.000057 mmole compound A and 1.1 mmole of MAO) wasmixed with 4 mL cyclohexane and was transferred to a 5 mL gas tightsyringe with long needle. This was brought out of the drybox and wasinjected into the reactor under nitrogen protection (positive nitrogenpressure). The reactor was pressured up with 1.2 MPa of nitrogen, thenreleased to 14 kPa. This was repeated one more time. Under stirring, thereactor was pressured up with ethylene to 1.2 MPa. The reaction mixturewas allowed to stir at between 70° C. to 97° C. for 60 min. Heatingsource was removed. Ethylene was vented to about 210 kPa. The reactorwas back filled with 1.4 MPa nitrogen and was released to 140 kPa. Thiswas repeated twice. The solution was poured into 300 mL methanol. Thepolymer was filtered, washed with 6×50 mL methanol and dried in vacuo.White polymer (19.7 g) was obtained. ¹HNMR in TCE-d₂ at 120° C.:34Me/1000CH₂. Mw=98,991; Mn=35,416(PDI=2.8). Density: 0.902g/cm³. MeltIndex: 1.03(190° C.). ¹³CNR(120° C.,TCE-d₂): Total Me was 29.4(Me=0;Et=10.8; Pr=0.0; Bu=6.0; Hex and higher=11.7).

EXAMPLES 25-30

In these Examples, all pressures are gauge pressures. The followingtransition metal compounds are used in the catalyst systems. A is anethylene oligomerization catalyst, while B is an ethylene and α-olefincopolymerization catalyst.

A is made by methods described in World Patent Application 99/02472,while B may be made as described in Ewen, et al., J. Am. Chem. Soc.,vol. 110, p. 6255-6256 (1988).

In these Examples, the following abbreviations are used:

DSC—differential scanning calorimetry

GPC—gel permeation chromatography

MAO—methylaluminoxane

MAO-IP—an MAO with improved toluene solubility

MI—melt index

Mn—number average molecular weight

Mw—weight average molecular weight

PE—polyethylene

PD—Mw/Mn

RT—room temperature

TCE—tetrachloroethane

The DSC was measured at a heating rate of 10° C./min, and the meltingpoints were taken as the peak of the melting endothermic on the secondheat. ¹³C NMR spectra were taken and interpreted generally as describedin World Patent Application 9623010. A Varian Unity® 400 MHz or a Bruker500 125 MHz spectrometer was used, using a 10 mm probe on typically10-15 weight percent polymer solutions. The MI was taken according toASTM method 1238, at a temperature of 190° C., using a 2.16 kg weight.Density by IR was determined by melt pressing films 0.2-0.3 mm (8-12mils) in thickness at 180° C. and cooled at approximately 15° C./min. inthe press. The IR spectrum of each film was obtained, and the peakabsorbance of the known crystalline band at approx. 1894 cm⁻¹ wasdetermined using a two-point baseline employing minima near 2100 and1850 cm³¹ ¹. The ratio of this absorbance to film thickness (in mils),termed the infrared crystallinity number (IRCN), was related to densityby a linear calibration. The method was calibrated by measuring the IRCNand gradient tube densities for melt pressed films of 24 commercial PEresins over a range of densities from 0.88 to 0.96. A linear fit to thedata (adjusted r²=0.993) gave the formula: density=6.9707*IRCN+0.8643.

EXAMPLE 77

A 600 mL Parr® reactor was cleaned, heated under vacuum and then allowedto cool under nitrogen. In a drybox, to a Hoke® cylinder was added 5 mLtoluene and 4.2 mL MAO(13.5wt % toluene solution). A (0.12 mg in 2 mLtoluene) and B (3.5 mg) were mixed with 150 mL 2,2,4-trimethyl pentanein a 300 mL RB flask. The flask was capped with a rubber septa. Both theHoke® cylinder and the flask were brought out of the drybox. Undernitrogen protection, the catalyst solution was cannulated to thereactor. The reactor was pressured with nitrogen and then the nitrogenpressure was released. The reactor was then pressured with ethylene andthe ethylene pressure was released. The reactor was heated to 65° C. andwas pressurized with 965 kPa ethylene. The MAO solution was added fromthe Hoke® cylinder at slightly higher pressure. The ethylene pressure ofthe reactor was then adjusted to 1.31 MPa. The reaction mixture wasallowed to stir for 25 min. The temperature of the reactor wascontrolled between 87 to 96° C. Heating source was removed. Ethylene wasvented to about 210 kPa. The reactor was back filled with 1.38 MPanitrogen and was vented to 210 kPa. This was done one more time. Thereaction mixture was cooled to RT. The reaction mixture was then slowlypoured into 400 mL methanol. After stirring at RT for 25 min, thepolymer was filtered, blended to small pieces, washed with methanol sixtimes and dried in vacuo. White polymer (24.0 g) was obtained.¹HNMR(TCE-d₂, 120° C.): 17Me/lOOOCH₂. GPC(PE standard, 135° C.):Mw=72,800; Mn=32,400; PD=2.2. Based on DSC, the polymer had two meltingpoints at 116° C. (14.8 J/g) and 103° C. (108.6 J/g). MI=0.40.

EXAMPLE 78

The supported catalyst was made by stirring a mixture of B (1.0 mg in 1mL toluene), 54.6 mg 0.1 wt % A in biphenyl, 0.35 g silica supported MAO(18 wt % Al) and 15 mL toluene. After shaking for 30 min, the solid wasfiltered, washed with 3×5 mL toluene and dried in vacuo for 1 h. It wasthen stored in a freezer and was used the same day.

A 600 mL Parr® reactor was cleaned and was charged with 150 g of wellbaked NaCl. It was dried under full vacuum at 120° C. for 2 h. It wasthen charged with 690 kPa of nitrogen while it was still hot. A waterbath was heated to 85° C. In a drybox, 0.66 mL 13.5 wt % MAO-IP toluenesolution was mixed with 4 mL of toluene. It was transferred to a 5 mLgas tight syringe. This was brought out of the drybox and the solutionwas injected into the autoclave under positive nitrogen pressure. Themixture was stirred (600 RPM) at 690 kPa nitrogen for 20 min. Stirringwas stopped. The reactor was then charged with 690 kPa of nitrogen. In adrybox, 110 mg of freshly made silica supported catalyst was mixed with4.5 mL cyclohexane. This was transferred to a 5 mL gas tight syringe. Itwas brought out of the drybox. The mixture was then injected into theautoclave under positive nitrogen pressure. The mixture was then allowedto stir (600 RPM) at 690 kPa nitrogen for 15 min. Stirring was stopped.Nitrogen was released to 14 kPa. The autoclave was evacuated under fullvacuum for 15 min, with stirring the last 5 min. It was recharged with1.17 MPa nitrogen, then released to 14 kPa, and this was repeated. Themixture was allowed to stir at 500 RPM. Ethylene pressure (2.41 MPa) wasapplied. The reactor was placed in the 85° C. water bath. The mixturewas allowed to stir at 90° C.-97° C. for 2 h. The RT mixture was mixedwith 800 mL water. The polymer was filtered, washed with water and wasblended into pieces with 400 mL water. It was then filtered, washed with3× water. The polymer was blended a few more times, followed by waterwash. It was then dried in vacuo. White polymer(26.6 g) was obtained.The small amount of leftover alphα-olefins were extracted using aSoxhlet extractor with hexanes. The polymer was then dried in vacuoovernight. Elemental analysis indicated that there was no salt (NaCl)left in the polymer. ¹HNMR(TCE-d₂, 120° C.): 20Me/1000CH₂. GPC(PEstandard, 135° C.): Mw=92,001; Mn=10,518; PD=8.8. The polymer had amelting point of 126° C. (74 J/g) based on DSC. MI=0.66. The density was0.919 based on IR.

EXAMPLE 79

The supported catalyst was made by stirring a mixture of B (1.0 mg in 1mL toluene), 109.2 mg 0.1 wt % A in biphenyl, 0.35 g silica supportedMAO (18wt % Al) and 15 mL toluene. After shaking for 30 min, the solidwas filtered, washed with 3×5 mL toluene and dried in vacuo for 1 h. Itwas then stored in a freezer and was used the same day.

A 600 mL Parr® reactor was cleaned and was charged with 150 g of wellbaked NaCl. It was dried under full vacuum at 120° C. for 2 h. It wasthen charged with 690 kPa of nitrogen while it was still hot. A waterbath was heated to 90° C. In a drybox, 0.50 mL 13.5 wt % PMAO-IP toluenesolution was mixed with 4 mL of toluene. It was transferred to a 5 mLgas tight syringe. This was brought out of the drybox and the solutionwas injected to the autoclave under positive nitrogen pressure. Themixture was stirred (600 RPM) at 690 kPa nitrogen for 20 min. Stirringwas stopped. In a drybox, 150 mg of freshly made silica supportedcatalyst was mixed with 4.5 mL cyclohexane. This was transferred to a 5mL gas tight syringe. It was brought out of the drybox. The mixture wasthen injected to the autoclave under positive nitrogen pressure. Themixture was then allowed to stir (600 RPM) at 690 kPa nitrogen for 15min. Stirring was stopped. Nitrogen was released to 14 kPa. Theautoclave was evacuated under full vacuum for 15 min, with stirring thelast 5 min. It was recharged with 1.17 MPa nitrogen, then released to 14kPa, and this was repeated. The mixture was allowed to stir at 500 RPM.Ethylene pressure (2.41 MPa) was applied. The reactor was placed in the90° C. water bath. The mixture was allowed to stir at 92° C.-95° C. for1 h, 56 min. Ethylene was then vented. The polymer/salt mixture wasstirred with 600 mL water for 20 min. The polymer was filtered, washedwith 3× water. The polymer was blended with 400 mL water, filtered,washed with 3× water, then stirred with 500 mL water for 1 h. This wasrepeated three times. An AgNO₃ test (for Cl) was negative at this point.The polymer was filtered, washed with water and then dried under fullvacuum in a 90° C. oil bath overnight. White polymer (58.1 g) wasobtained. The small amounts of leftover alph α-olefins were extractedusing a Soxhlet extractor with hexanes. The polymer was then dried invacuo overnight. Elemental analysis indicated that there was no salt(NaCl) left in the polymer. ¹HNMR(TCE-d₂, 120° C.): 19Me/1000CH₂. GPC(PEstandard, 135° C.): Mw=104,531; Mn=13,746; PD=7.6. The polymer had twomelting points at 125° C. (85.8 J/g) and 101° C. (25 J/g) based on DSC.MI=0.96. The density was 0.912 based on IR.

EXAMPLE 80

The supported catalyst was made by stirring a mixture of B (1.0 mg in 1mL toluene), 54.6 mg 0.1 wt % A in biphenyl, 0.35 g silica supported MAO(18 wt % Al) and 15 mL toluene. After shaking for 30 min, the solid wasfiltered, washed with 3×5 mL toluene and dried in vacuo for 1 h. It wasthen stored in a freezer and was used the same day.

A 600 mL Parr® reactor was cleaned and was charged with 150 g of wellbaked NaCl. It was dried under full vacuum at 120° C. for 2 h. It wasthen charged with 690 kPa of nitrogen while it was still hot. An oilbath was heated to 85° C. In a drybox, 0.66 mL 13.5 wt % MAO-IP intoluene solution was mixed with 4 mL of toluene. It was transferred to a5 mL syringe. This was brought out of the drybox and the solution wasinjected into the autoclave under positive nitrogen pressure. Themixture was stirred (600 RPM) at 690 kPa nitrogen for 20 min. Stirringwas stopped. In a drybox, 60 mg of freshly made silica supportedcatalyst was mixed with 4.5 mL cyclohexane. This was transferred to a 5mL gas tight syringe. It was brought out of the drybox. The mixture wasthen injected into the autoclave under positive nitrogen pressure. Themixture was then allowed to stir (600 RPM) at 690 kPa nitrogen for 15min. Stirring was stopped. Nitrogen was released to 14 kPa. Theautoclave was evacuated under full vacuum for 15 minutes, with stirringthe last 5 min. It was recharged with 1.17 MPa nitrogen, then releasedto 14 kPa, and this was repeated once. The mixture was allowed to stirat 500 RPM. Ethylene pressure (2.41 MPa) was applied. The reactor wasplaced in the 85° C. oil bath. The mixture was allowed to stir at 75°C.-85° C. for 1 h, then at 110° C.-115° C. for 2 hr. Ethylene wasvented. The polymer/salt mixture was stirred with 600 mL water for 20min. Polymer was filtered, and washed with 3× water. The polymer wasblended with 400 mL water, filtered, washed with 3× water. The polymerwas blended and washed again. It was then dried in vacuo overnight.White polymer (22.7 g) was obtained. ¹HNMR(TCE-d₂, 120° C.):23Me/1000CH₂. GPC(PE standard, 135° C.): Mw=107,173; Mn=25,054; PD=4.3.The polymer had two melting points at 126° C. (32.9 J/g) and 114° C.(50.7 J/g) based on DSC. MI=2.0. The density was 0.919 based on IR.

EXAMPLE 81

The supported catalyst was made by stirring a mixture of B (0.25 mg in 1mL toluene), 27.2 mg 0.1 wt % A in biphenyl, 0.35 g silica supported MAO(18 wt % Al) and 15 mL toluene. After shaking for 30 min, the solid wasfiltered, washed with 3×5 mL toluene and dried in vacuo for 1 h. It wasthen stored in a freezer and was used the same day.

A 600 mL Parr® reactor was cleaned and was charged with 150 g of wellbaked NaCl. It was dried under full vacuum at 120° C. for 2 h. It wasthen charged with 690 kPa of nitrogen while it was still hot. A waterbath was heated to 85° C. In a drybox, 0.66 mL 13.5 wt % PMAO-IP intoluene solution was mixed with 4 mL of toluene. It was transferred to a5 mL syringe. This was brought out of the drybox and the solution wasinjected to the autoclave under positive nitrogen pressure. The mixturewas stirred (600 RPM) at 690 kPa nitrogen for 30 min. Stirring wasstopped. In a drybox, 200 mg of freshly made silica supported catalystwas mixed with 4.5 mL cyclohexane. This was transferred to a 5 mL gastight syringe. It was brought out of the drybox. The mixture was theninjected to the autoclave under positive nitrogen pressure. The mixturewas then allowed to stir (600 RPM) at 690 kPa nitrogen for 15 min.Stirring was stopped. Nitrogen was released to 14 kPa. The autoclave wasevacuated under full vacuum for 15 min, with stirring the last 5 min. Itwas recharged with 1.17 MPa nitrogen, then released to 14 kPa, and thiswas repeated once. The mixture was allowed to stir at 500 RPM. Ethylenepressure (2.41 kPa) was applied. The reactor was placed in the 85° C.water bath. The mixture was allowed to stir at 85° C.-93° C. for 2 h.Ethylene was then vented. The polymer/salt mixture was stirred with 600mL water for 20 min. Polymer was filtered, washed with 3× water. Thepolymer was blended with 400 mL water, filtered, and washed with 3×water. The polymer was blended, filtered and washed again. It was thendried in vacuo overnight. White polymer (12.7 g) was obtained.¹HNMR(TCE-d₂, 120° C.) 25Me/1000CH₂. GPC(PE standard, 135° C.):Mw=116,721; Mn=43,094; PD=2.7. The polymer had two melting points at122° C. (73.2 J/g) and 91° C. (73.1 J/g) based on DSC. MI=0.42. Thedensity was 0.921 based on IR.

Using data from the GPC and ¹³C NMR analyses one can calculate a rough Kfactor for the oligomerization of the ethylene to α-olefin. Based on theMn, the polymer should have 0.6 ends of chains for each 1000 CH₂ groups,so the actual level of Hex+ branches in this polymer, excluding ends ofchains, is 12.6. Based on 4.4 butyl branches/1000 CH₂ groups and 11.5Hex+ branches/1000 CH₂ groups, one can calculate that the K constant wasabout 0.64. As noted above this calculation is subject to several errorsand should only be considered approximate.

Table 11 lists the branching distributions of the above preparedpolymers, as determined by ¹³C NMR. No branches containing odd numbersof carbon atoms were detected. The branching levels for Hex+ includeends-of-chains.

TABLE 11 Ex. No. 77 78 79 80 81 Et* 6.5 5.4 6.6 4.6 4.9 Bu** 3.2 4.1 4.14.0 4.4 Hex⁺*** 6.5 9.2 9.7 9.6 13.2  Hex⁺/Bu 2.0 2.2 2.4 2.4 3.0Hex⁺/Et 1.0 1.7 1.5 2.1 2.7 *, **, ***correspond to 1-butene, 1-hexene,1-octene and longer olefins, respectively. No odd numbered branches weredetected by ¹³CNMR

EXAMPLE 82

Rheological measurements were performed on some of the above polymers,as well as two comparative polymers. One of these was DuPont 2020polyethylene, a low density polyethylene available from E. I. DuPont deNemours & Co., Wilmington, DE 19898 U.S.A. The other comparative polymerwas a LLDPE, Exceed® 350D60 available from Exxon Chemical., Inc.,Houston, Tex., U.S.A., reported to be a copolymer of ethylene and1-hexene, and to have a density of 0.917 g/cm³. This sample had an Mw of112,000, as determined by light scattering.

A Bohlin CSM rheometer (Bohlin Instruments, Inc., Cranbury, N.J. 08512U.S.A.) was used in the parallel plate mode with 25 mm diameter platesand 1 mm gap to make rheological measurements. Each molded sample wasbathed in a nitrogen atmosphere and measurements were carried out at140° C. after briefly heating to 190° C. to remove any traces ofcrystallinity. Measurements were made in the oscillatory mode between0.001 and 30 Hz. The maximum stress applied was 2000 Pa and thecollected data was always in the linear viscoelastic region. On the samesample, creep/recoil experiments at very low stress (10 Pa) were alsoperformed immediately following the oscillatory flow. Measurements weremade over 19 h to determine melt stability via viscosity and elasticitychanges.

A special stabilizer package, sample loading and molding procedure wereused. Ten ml of a stabilizer solution (0.2 g each of Irganox® 1010,Irganox® 1076 and Irgafos® 168 in 100 ml hexane) was squirted onto 1.2 gof pellets. Following air drying, the sample was placed overnight in avacuum oven at 50° C. with nitrogen bleed. The polymer was then loadedinto a cold vacuum mold. Vacuum was applied (pressure no greater than1.3 kPa absolute) to the mold using a gasket to seal against aircontamination. The evacuated mold was heated to 140° C., pressureapplied followed by a quench cool to RT. Pressure was released at thispoint and the sample removed from the mold and placed immediately intothe RT rheometer. The sample was then rapidly heated to 190° C. (thistook about 5 min) then rapidly cooled (another 10 min) back to themeasurement temperature prior to trimming, equilibration at themeasurement temperature for about 15 min, and making measurements. Theoscillatory flow experiments were performed first; they took about 1.5h. These were followed immediately by the creep/recoil experiments whichtook about 16 additional h. Two identical creep/recoil experiments weredone with 8 ks and 20,000 ks creep and recoil times, respectively. Theentire rheometer was bathed in nitrogen and nitrogen was also applied tothe rheometer air bearing. Our experience indicates that small amountsof air contamination with hydrocarbon polymers resulted in sampledegradation. Two separate moldings and measurements were made per sampleand the results shown are the averaged results shown in FIG. 1. FIG. 1shows the complex viscosity of the polymers versus frequency of therheometer, which is a measure of shear, higher frequencies being highershear rates. Many of the polymers of the Examples above have viscosityprofiles similar to the DuPont 2020 LDPE, an excellent processingpolymer.

Some of these polymers were also analyzed by SEC (same as GPC) and MALS,multiangle light scattering, and at the same time viscometry, to obtainintrinsic viscosity, Mw, and radius of gyration. The weight averagedmolecular weights (Mw) and intrinsic viscosities([η]) were determinedusing a Wyatt Technology (Santa Barbara, Calif. 93117 U.S.A.) Dawn® DSPlight scattering photometer and Viscotek (Houston, Tex. 77060 U.S.A.)210R viscometer, respectively. Both of these were connected to a liquidchromatograph (Polymer Laboratories, (Amherst, Mass. 01002 U.S.A.)PL210, also called SEC or GPC). Eluent from the SEC is directed to thelight scattering instrument through a heated transfer line (alsocontrolled at 150° C.) and then back into the PL210. The oven in thePL210 houses both the differential refractometer and the 210R viscometeras well as the SEC columns. The light scattering instrument employs anAr ion laser at 488 nm. A single dn/dc of −0.100 (mL/g) (determined frommany additional analyses) was used for all calculations. The actualconcentration eluting from the column was determined from the calibrateddifferential refractometer using the dn/dc value of −0.100. In allcases, the integrated concentration was within 2-5% of the weighed massof polymer injected. The solvent used was 1,2,4-trichlorobenzene;stabilized with 0.05% BHT. A temperature of 150° C. was used fordissolution of solutions and for analysis. Solutions were prepared insmall (2 mL) vials at known concentrations of 0.1-0.15%, left in sealedvials in a heating block for 8-12 hours to dissolve, and then analyzed.Polymer solutions were not filtered prior to analysis. Injection volumewas 200 microliters, resulting in the injection of 1-1.5 mg for eachanalysis. Results were obtained using software available from WyattTechnology. The average intrinsic viscosity, [η], was obtained by takingthe ratio of the integrated viscometer peak and the integrateddifferential refractometer peak. Intrinsic viscosity results and Mwvarious polymers are shown in Table 12.

The results of the Mw and intrinsic viscosity analyses are also plottedin FIG. 2, along with the results from other polyethylenes andhydrogenated poly(1,3-butadiene) (PB), a linear polymer which is thesame (after hydrogenation) as polyethylene. It is clear that at a givenMw, many of the polymers used herein have a lower intrinsic viscosity ata given Mw than linear polyethylene or polyethylenes containing onlyshort chain branching (LLDPE).

TABLE 12 Polymer S_(T) P_(R) Mw [η] Example 77  86000 1.18 Example 78≧0.61 14.4 116000 1.10 Example 79 ≧1.8 52.6 150000 1.25 Example 80 ≧1.652.1 156000 1.19 Example 81 ≧3.8 190 193000 1.38 Exxon Exceed ® 350D601.00 7.95 112000 1.69 DuPont 2020 LDPE 0.19 69.9 278000 1.00

What is claimed is:
 1. A polyethylene having a structural index, S_(T),of about 1.4 or more.
 2. The polyethylene as recited in claim 1 whereinthe structural index is about 2.0 or more.